CN-121974837-A - Dithiocarbonate sulfonate, preparation method thereof and copper plating solution

CN121974837ACN 121974837 ACN121974837 ACN 121974837ACN-121974837-A

Abstract

The application relates to the technical field of electroplating, in particular to dithiocarbonate sulfonate, a preparation method thereof and copper plating solution. The preparation method of the dithiocarbonate sulfonate comprises the following steps of preparing alkaline alcohol liquid, adding carbon disulfide into the alkaline alcohol liquid, enabling a certain content of the alcohol compound to undergo nucleophilic addition reaction with the carbon disulfide to generate dithiocarbonate, dissolving the dithiocarbonate into the residual alcohol compound to obtain reaction liquid, adding a sultone compound into the reaction liquid, enabling the dithiocarbonate and the sultone compound to undergo nucleophilic substitution reaction, and generating and separating out the dithiocarbonate sulfonate. The application enriches the synthetic route of dithiocarbonate sulfonate, and the synthesized compound can meet the performance requirement of copper plating brightening agent.

Inventors

WU HAOZHONG
LIU BINYUN
TAN CHAOLI
LI JINGYA
ZOU HAOBIN
XIAO DINGJUN

Assignees

广东光华科技股份有限公司
光华科学技术研究院(广东)有限公司
广东东硕科技有限公司

Dates

Publication Date: 20260505
Application Date: 20260120

Claims (10)

1. A process for the preparation of dithiocarbonate sulfonates comprising the steps of: preparing an alkaline alcohol solution, wherein the alkaline alcohol solution comprises an alcohol compound, and the structure of the alcohol compound is that ; Adding carbon disulfide into the alkaline alcohol solution, and carrying out nucleophilic addition reaction on a certain content of alcohol compounds and the carbon disulfide to generate dithiocarbonate, wherein the dithiocarbonate is dissolved in the residual content of alcohol compounds to obtain a reaction solution, and the dithiocarbonate comprises the following groups: ; Adding a sultone compound into the reaction liquid, wherein the sultone compound has the structure as follows: the dithiocarbonate and the sulfonate lactone compound undergo nucleophilic substitution reaction to generate and precipitate dithiocarbonate sulfonate, and the dithiocarbonate sulfonate comprises the following groups: ; Wherein R is selected from C 1-12 alkyl substituted or unsubstituted with C 1-12 alkoxy, C 3-12 cycloalkyl substituted or unsubstituted; y is selected from- (CH 2 ) n -; n is 3 or 4.
2. The method for producing dithiocarbonate sulfonate according to claim 1, wherein the alcohol compound is at least one selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, n-hexanol, cyclopentanol, cyclohexanol, and ethylene glycol mono-n-propyl ether.
3. The method for producing dithiocarbonate sulfonate according to claim 1, wherein the basic alcohol solution comprises a basic substance which is dissolved in the alcohol compound or dispersed in the alcohol compound.
4. The method for producing dithiocarbonate sulfonate according to claim 3, wherein the ratio of the volume of the alcohol compound to the number of moles of the basic substance is (0.5 to 10) mL/1 mmol.
5. The method for producing dithiocarbonate sulfonate according to claim 3, wherein the basic alcohol solution is produced by mixing the alcohol compound with the basic substance or adding an alkali metal to the alcohol compound and reacting the mixture to produce the basic substance.
6. The method of preparing dithiocarbonate sulfonate according to claim 5, comprising at least one of the following features: (1) The alkaline substance is at least one of inorganic alkali and organic alkali, the inorganic alkali is at least one of sodium hydroxide and potassium hydroxide, and the organic alkali is at least one of sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide and potassium tert-butoxide; (2) The molar ratio of the alkaline substance to the carbon disulfide to the sultone compound is 1 (1.00-1.05): 1.00-1.20.
7. The method of preparing dithiocarbonate sulfonate according to claim 5, comprising at least one of the following features: (1) The alkali metal is at least one selected from sodium and potassium; (2) The molar ratio of the alkali metal to the carbon disulfide to the sultone compound is 1 (1.00-1.05): 1.00-1.20.
8. The method for producing dithiocarbonate sulfonate according to any one of claims 1 to 7, comprising at least one of the following features: (1) Adding the carbon disulfide into the alkaline alcohol solution for 30-120 min; (2) The reaction temperature for nucleophilic addition reaction is 5-20 ℃; (3) The nucleophilic addition reaction takes place for 60-90 min; (4) The time for adding the sultone compound into the reaction liquid is 60-120 min; (5) The reaction temperature for nucleophilic substitution reaction is 15-35 ℃; (6) The nucleophilic substitution reaction takes place for 120-180 min.
9. Dithiocarbonate sulfonate, prepared by the preparation method according to any one of claims 1 to 8.
10. A copper plating solution comprising the dithiocarbonate sulfonate of claim 9.

Description

Dithiocarbonate sulfonate, preparation method thereof and copper plating solution Technical Field The application relates to the technical field of electroplating, in particular to dithiocarbonate sulfonate, a preparation method thereof and copper plating solution. Background The copper layer can be formed by electroplating the copper plating solution. Additives are generally added into the copper plating solution, and the additives play a critical role in the electroplating process and mainly comprise a brightening agent, an inhibitor and a leveling agent, wherein the brightening agent, the inhibitor and the leveling agent are adsorbed on the surface of a cathode to influence the reduction process of copper ions, so that the quality and the performance of an electroplated copper layer are controlled. Wherein the brightening agent is usually a sulfur-containing compound, and has the effects of reducing cathode polarization, accelerating nucleation and promoting copper deposition. The brightening agent is controlled within a certain concentration range, so that the crystallization mode of copper can be influenced, and the plating layer is refined in crystal grain, compact in structure and bright in surface. The brightening agents which are used for acidic copper plating solutions at present are some sulfur-containing sulfonates, and sulfur-containing groups include mercapto groups, disulfide groups, dithiocarbamates and dithiocarbonates. Wherein the representative of the sulfonate containing mercapto group is sodium 3-mercaptopropane sulfonate (MPS), the representative of the sulfonate containing disulfide is sodium polydithio-dipropane sulfonate (SPS), and the representative of the sulfonate containing dithiocarbamate is N, N-dimethyl-dithiocarbamic acid- (3-sulfopropyl) ester (DPS). The structures and the synthesis methods of the above representatives are reported in the corresponding documents or patents, however, the structures and the synthesis reports of dithiocarbonate sulfonate are less, and it is necessary to design a synthetic route of dithiocarbonate sulfonate to produce a compound suitable as a brightening agent for an acidic copper plating solution. Disclosure of Invention Based on the above, the first aspect of the application provides a preparation method of dithiocarbonate sulfonate, which adopts the following technical scheme: a process for the preparation of dithiocarbonate sulfonates comprising the steps of: preparing an alkaline alcohol solution, wherein the alkaline alcohol solution comprises an alcohol compound, and the structure of the alcohol compound is that ; Adding carbon disulfide into the alkaline alcohol solution, and carrying out nucleophilic addition reaction on a certain content of the alcohol compound and the carbon disulfide to generate dithiocarbonate, wherein the dithiocarbonate is dissolved in the residual content of the alcohol compound to obtain a reaction solution, and the dithiocarbonate comprises the following groups:; Adding a sultone compound into the reaction liquid, wherein the sultone compound has the structure as follows: the dithiocarbonate and the sulfonate lactone compound undergo nucleophilic substitution reaction to generate and precipitate dithiocarbonate sulfonate, and the dithiocarbonate sulfonate comprises the following groups: ; Wherein R is selected from C 1-12 alkyl substituted or unsubstituted with C 1-12 alkoxy, C 3-12 cycloalkyl substituted or unsubstituted; y is selected from- (CH 2)n -; n is 3 or 4. In a second aspect the present application provides a dithiocarbonate sulfonate prepared by the preparation process as described above. The third aspect of the present application provides a copper plating solution comprising the dithiocarbonate sulfonate as described above. Compared with the traditional scheme, the application has the following beneficial effects: The application provides a method for synthesizing dithiocarbonate sulfonate, which comprises the steps of firstly utilizing alcohol compounds with certain content and carbon disulfide to generate corresponding dithiocarbonate under alkaline environment, wherein the salt can be dissolved in unreacted alcohol compounds, and reacting to obtain reaction liquid containing dithiocarbonate. Then, a sultone compound is added into the reaction liquid, nucleophilic substitution reaction is carried out on the sultone compound and dithiocarbonate, so that dithiocarbonate sulfonate which is indissoluble in alcohol compounds is generated and separated out, and carbon disulfide, intermediate dithiocarbonate and sultone compound which are not reacted and are dissolved in the alcohol compounds can be removed together through simple filtering operation, thus obtaining the dithiocarbonate sulfonate with high purity. The method enriches the synthetic route of the dithiocarbonate sulfonate, enriches the diversity of the dithiocarbonate sulfonate structure, and the synthesized compound can meet the performa